Liquid composition, and resistor film, resistor element and circuit board using same

ABSTRACT

There is provided a liquid composition that can form a resistor exhibiting a stable resistance value. One mode of the liquid composition of the invention is a liquid composition comprising (a) an epoxy resin, (b) carbon black particles, (c) carbon nanotubes and (d) a solvent with a vapor pressure of less than 1.34×10 3  Pa at 25° C.

TECHNICAL FIELD

The present invention relates to a liquid composition, and to a resistorfilm, a resistor element and a circuit board using it.

BACKGROUND ART

Multilayer printed circuit boards have conventionally been produced bysteps including preparing a stack in which a plurality of one-sidedprinted circuit boards or double-sided printed circuit boards having acircuit formed by etching, are laminated by pressing via an adhesivelayer such as a glass woven fabric prepreg, and a hole is opened in thestack using a drill or laser, after which a conductive layer is formedon the hole walls by plating or the like for electrical connectionbetween the layers.

In recent years, methods of directly forming wiring patterns by printingmethods are being investigated as substitutes for the conventionalmethods of producing multilayer printed circuit boards using etching orplating. For example, a method of forming a wiring pattern by ink jetprinting (Patent document 1) and a method of producing a multilayerprinted circuit board by forming a conductive layer and a hole-formedinsulating layer on a substrate by a printing method (Patent document 2)have been proposed.

With these production methods, it is possible to produce a multilayerprinted circuit board without using large-scale equipment such aspressing and plating equipment. An additional advantage is very highmaterial usage efficiency, because the conductor ink or insulator inkcan be printed only on the necessary sections.

At the same time, advances are being made in thickness reduction andhigh densification of circuit boards, to meet the needs forminiaturization and lighter weights of electronic devices in recentyears. In addition, for electronic devices in the fields of datatransmission and information processing, it is becoming ever moreessential to accomplish efficient securing of mounting areas formounting of high-performance parts. In the attempt to secure mountingareas, research has been carried out on miniaturization of surfacemounting parts, narrow-pitch formation of terminals and fine patterningof boards, SMT (surface mounting technology) for high-density mountingof parts on board surfaces, and Advanced SMT which is a higher level ofthe same technology.

However, the numbers of active element parts (chip parts) have beenincreasing to meet the needs of higher functioning for electronicdevices. As the number of passive element parts (capacitors, inductorsand registers) that perform electrical regulating is likewiseincreasing, the mounting areas of such passive element parts oftenoccupy more than half of the entirety. This has constituted an obstacleagainst miniaturization and higher performance of electronic devices.

Techniques for building passive element functions into boards are alsobeing investigated. Such techniques promise not only miniaturization,but also effects such as improved reliability, by eliminating theconventional solder joints used for electrical connection betweensurface mounting parts and circuit boards, increased freedom of circuitdesign, improved electrical characteristics by reducing parasiticcapacitance since passive elements can be effectively positionedinternally, thereby shortening wiring lengths, and lower cost byeliminating the need for surface mounting.

Passive element-forming materials have therefore been developed with thepurpose of providing passive element functions inside boards. Forexample, materials plated with relatively high-resistance metals havebeen used as resistors for built-in passive elements (Patent documents 3and 4). There has also been proposed a method of forming resistors byink jet printing, without the process of plating or etching (Non-patentdocument 1).

The present inventors have also proposed an ink comprising carbon blackparticles dispersed in a thermosetting resin, as a material that allowsresistors of desired sizes to be formed at desired locations using anink-jet apparatus (Patent document 5).

CITATION LIST Patent Literature

-   [Patent document 1] Japanese Unexamined Patent Application    Publication No. 2003-80694-   [Patent document 2] Japanese Unexamined Patent Application    Publication No. 2003-110242-   [Patent document 3] Japanese Examined Patent Application Publication    SHO No. 57-3234-   [Patent document 4] U.S. Pat. No. 3,808,576-   [Patent document 5] Japanese Unexamined Patent Application    Publication No. 2007-165708

Non-Patent Literature

-   [Non-patent document 1] “Breakthrough in device miniaturization with    ink-jet printing”, Nikkei Electronics, 2002, No. 6/17, p. 67-78

SUMMARY OF INVENTION Technical Problem

Patent document 1, however, mentions nothing regarding the ink that isto be used. Also, Patent document 2, while mentioning that athermosetting resin is used in the ink for insulating layer formation,does not contain any specific reference to the ink viscosity or resincomposition, or to inks having functions other than insulating layerformation. In addition, while Non-patent document 1 proposes forming aresistor by ink jet printing, it does not specifically mention the inkused to form the resistor.

Methods for forming resistors by offset printing have also been proposedin the prior art, but the inks used generally have viscosity higher than20 Pa·s and a thixotropic property. Furthermore, inks for offsetprinting comprise conductive particles with mean particle sizes of 1 μmor greater, and such inks cannot be applied for ink jet printing. Theinks used for ink jet printing are commonly preferred to have lowviscosity, due to restrictions in the ink-jet head discharge system.When particles are included, the dispersion particle sizes arepreferably small from the viewpoint of preventing nozzle clogging.

In light of these demands, the present inventors have proposed an inkcomprising carbon black particles dispersed in a thermosetting resin(see Patent document 5, for example). The ink allows formation ofresistors of prescribed sizes at prescribed locations using an ink-jetapparatus. Depending on the carbon black particles used, however, theresistance value is often unstable after curing and the resistance maydiffer even between different test pieces formed to the same shape. Inaddition, because a stable low resistance value is exhibited utilizingthe percolation structure of the carbon black particles, a given type ofcarbon black particles can only exhibit a specific resistance value, andit has been necessary to select a new carbon black particle type toobtain a different resistance value (volume resistivity). In such cases,the new carbon black particles must be freshly examined for theirdispersion stability and resistance value, as well as their ability toexhibit a stable resistance value, and this has been an obstacle againstrapid material development.

The present invention has been accomplished in light of this problem,and its object is to provide a liquid composition that is suitable forforming resistors by ink jet printing and that can exhibit a stableresistance value, as well as a resistor film, resistor element andcircuit board using the liquid composition.

Solution to Problem

In order to achieve the object stated above, the invention provides thefollowing [1] to [22].

[1] A liquid composition comprising (a) an epoxy resin, (b) carbon blackparticles, (c) carbon nanotubes and (d) a solvent with a vapor pressureof less than 1.34×10³ Pa at 25° C.[2] A liquid composition according to [1] above, wherein the meandispersion particle size of the (b) carbon black particles is no greaterthan 500 nm, and the maximum dispersion particle size is no greater than2 μm.[3] A liquid composition according to [1] or [2] above, wherein theouter diameter of the (c) carbon nanotubes is 3 nm or greater and thelength is 100 nm or greater.[4] A liquid composition according to any one of [1] to [3] above,wherein the content of the (b) carbon black particles is 10 to 80 vol %,based on the total solid volume of the liquid composition.[5] A liquid composition according to any one of [1] to [4] above,wherein the content of the (c) carbon nanotubes is 0.1 to 20 parts bymass with respect to 100 parts by solid mass of the (b) carbon blackparticles.[6] A liquid composition according to any one of [1] to [5] above,wherein the viscosity is no greater than 50 mPa·s at 25° C.[7] A liquid composition according to any one of [1] to [6] above,wherein the (a) epoxy resin is a glycidyl etherified condensationproduct of a phenol and an aldehyde.[8] A liquid composition according to any one of [1] to [7] above, whichfurther comprises (e) a curing agent, the (e) curing agent comprisingthe condensation product of a phenol and an aldehyde.[9] A liquid composition comprising (a1) a diol with a molecular weightof 40 or greater and less than 1000 and/or a resin containing the diolas a backbone, and (b) carbon black particles.[10] A liquid composition according to [9] above, wherein the (a1) diolwith a molecular weight of 40 or greater and less than 1000 and/or aresin containing the diol as a backbone includes (a2) an epoxy resinwith a molecular weight of between 200 and 50,000, comprising a diolwith a molecular weight of 40 or greater and less than 1000 in thebackbone.[11] A liquid composition according to [9] or [10] above, which furthercomprises (d) a solvent with a vapor pressure of less than 1.34×10³ Paat 25° C., and (e) a curing agent.[12] A liquid composition according to [11] above, wherein the (e)curing agent comprises the condensation product of a phenol and analdehyde.[13] A liquid composition according to any one of [9] to [12] above,wherein the mean dispersion particle size of the (b) carbon blackparticles is no greater than 500 nm, and the maximum dispersion particlesize is no greater than 2[14] A liquid composition according to any one of [9] to [13] above,wherein the content of the (b) carbon black particles is 10 to 80 vol %,based on the total solid volume of the liquid composition.[15] A liquid composition according to any one of [9] to [14] above,wherein the viscosity is no greater than 50 mPa·s at 25° C.[16] A liquid composition according to any one of [9] to [15] above,which further comprises (c) carbon nanotubes.[17] A liquid composition according to [16] above, wherein the outerdiameter of the (c) carbon nanotubes is 3 nm or greater and the lengthis 100 nm or greater.[18] A liquid composition according to [16] or [17] above, wherein thecontent of the (c) carbon nanotubes is 0.1 to 20 parts by mass withrespect to 100 parts by solid mass of the (b) carbon black particles.[19] A resistor film formed by removing the solvent from a liquidcomposition according to any one of [1] to [18] above by heating.[20] A resistor film formed by printing or coating a liquid compositionaccording to any one of [1] to [18] above on a substrate to form a filmof the liquid composition, and removing the solvent from the film of theliquid composition by heating.[21] A resistor element having a resistor film according to [19] or [20]above.[22] A circuit board having a resistor element according to [21] aboveformed on a substrate.

Advantageous Effects of Invention

According to the invention it is possible to provide a liquidcomposition that is suitable for forming resistors by ink jet printingand that can exhibit a stable resistance value, as well as a resistorfilm, resistor element and circuit board using the liquid composition.The liquid composition of the invention also allows the resistance valueto be varied by addition of CNT and selection of the resin composition,without completely retesting new carbon black particles. In addition, byusing the liquid composition of the invention it is possible to form aresistor on a board by the simple method of ink jet printing, while alsoreducing environmental load created when using solder and the like, andfacilitating formation of boards with built-in passive elementfunctions.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a perspective view of an embodiment of a circuit board of theinvention.

FIG. 2 is an end view of FIG. 1 along line II-II.

FIG. 3 is a graph showing the relationship between heat curing time andvolume resistivity for the liquid compositions of the examples andcomparative examples.

FIG. 4 is a graph showing the relationship between heat curing time andvolume resistivity for the liquid compositions of the examples andcomparative examples.

DESCRIPTION OF EMBODIMENTS

Embodiments of the invention will now be described in detail. However,the present invention is not limited to the embodiments described below.

The liquid composition according to a first embodiment of the inventioncomprises (a) an epoxy resin, (b) carbon black particles, (c) carbonnanotubes and (d) a solvent with a vapor pressure of less than 1.34×10³Pa at 25° C., and also preferably (e) a curing agent.

The liquid composition according to a second embodiment of the inventioncomprises (a1) a diol with a molecular weight of 40 or greater and lessthan 1000 and/or a resin comprising the diol as a backbone (comprising adiol residue) and (b) carbon black particles, and preferably furthercomprises at least one of (c) carbon nanotubes, (d) a solvent with avapor pressure of less than 1.34×10³ Pa at 25° C., and (e) curingagents. The (a1) diol with a molecular weight of 40 or greater and lessthan 1000 and/or a resin containing the diol as a backbone preferablyincludes (a2) an epoxy resin with a molecular weight of between 200 and50,000, comprising a diol with a molecular weight of 40 or greater andless than 1000 in the backbone (comprising a diol residue).

The liquid compositions according to the first and second embodimentsmay be suitably used to form resistors by a printing method such as inkjet printing, and both of the compositions contain carbon blackparticles. The components to be used in the liquid compositions of thefirst and second embodiments will now be explained.

The primary particle size of the (b) carbon black particles ispreferably no greater than 100 nm, more preferably no greater than 80 nmand even more preferably no greater than 50 nm, from the viewpoint ofadjusting the viscosity of the liquid composition to a viscositysuitable for printing, and from the viewpoint of exhibiting theresistance value with cured products. The primary particle size of the(b) carbon black particles is also preferably 10 nm or greater.

The dispersion particle size of the (b) carbon black particles affectsthe printability and resistance value stability. Therefore, the meandispersion particle size of the (b) carbon black particles in the liquidcomposition is preferably no greater than 1000 nm, more preferably nogreater than 500 nm and even more preferably no greater than 300 nm.Also, the maximum dispersion particle size of the (b) carbon blackparticles is preferably no greater than 5 μm, more preferably no greaterthan 2 μm and even more preferably no greater than 1 μm. If the meandispersion particle size of the (b) carbon black particles is greaterthan 1000 nm or the maximum dispersion particle size is greater than 5μm, clogging of the ink-jet head nozzle may occur and it will tend to beimpossible to accomplish stable printing, when it is attempted todischarge the liquid composition by ink jet printing.

The mean dispersion particle size of the (b) carbon black particles ispreferably 10 nm or greater. The maximum dispersion particle size of the(b) carbon black particles is also preferably 10 nm or greater.

Throughout the present specification, “dispersion particle size” refersto the particle size of particles that are dispersed in a liquid, andthe values used in the present specification were measured using asubmicron particle analyzer (Model N5) by Beckman Coulter, Inc.

The amount of (b) carbon black particles added is preferably 10 to 80vol % and more preferably 10 to 70 vol %, based on the total solidvolume of the liquid composition (the total solid volume remaining afterremoval of the solvent). If the amount added is less than 10 vol %, itwill tend to be difficult to obtain the desired volume resistivity. Ifthe amount of addition exceeds 80 vol %, problems will tend to result,such as increased viscosity of the liquid composition, and inability tomaintain the strength of the resistor film after film formation.

The liquid composition of the invention may also comprise (c) carbonnanotubes (hereunder, “CNT”). The liquid composition of the firstembodiment comprises CNT as an essential component, while the liquidcomposition of the second embodiment preferably comprises CNT. If theliquid composition comprises CNT, it will be possible to form a resistorwith a lower and more stable resistance value.

CNT are largely of two types, single-walled (monolayer) and multi-walled(multilayer) types, and either CNT type may be used according to theinvention. The outer diameter of the CNT is preferably 3 nm or greater.The length of the CNT is preferably 100 nm or greater and morepreferably 300 nm or greater. This preferred dimensional range is inconsideration of bridging between carbon black particles by the CNT. Inorder to ensure a satisfactory discharge property in an ink-jetapparatus, on the other hand, the length of the CNT is preferably nogreater than 15 μm and the outer diameter of the CNT is preferably nogreater than 1000 nm. When synthesized, CNT is generally in the form ofgroups of multiple CNTs known as “bundles”. The bundles may be in anystate so long as they are consistent throughout the material used, andin order to obtain a lower resistance value with the same amount ofaddition, the bundles are preferably loose. The CNT are preferablyprovided in the form of a dispersion, although this is not limitative.Using a dispersion state is preferred, since it can avoid adverseeffects on the other materials during dispersion (for example, crushingof the particles or contamination with foreign components). The CNTdispersion used preferably comprises the CNT dispersed in the samesolvent used to dissolve the resin or a solvent that is compatible withthat solvent, from the viewpoint of ensuring stability of thedispersion.

The amount of CNT added is preferably 0.1 to 20 parts by mass and morepreferably 0.1 to 10 parts by mass, with respect to 100 parts by solidmass of the (b) carbon black particles (solid mass remaining afterremoval of the solvent). If the amount of CNT addition is less than 0.1part by mass, it will tend to be difficult to obtain a resistor withlower and more stable volume resistivity. If the amount of CNT additionis greater than 20 parts by mass, the viscosity of the liquidcomposition will increase more readily, and the potential for problemswith the ink-jet discharge property will tend to increase.

The (a) epoxy resin to be used in a liquid composition according to thefirst embodiment may be, for example, a bisphenol A-type epoxy resin; abisphenol F-type epoxy resin; a bisphenol S-type epoxy resin; abiphenol-type epoxy resin; an alicyclic epoxy resin; an aliphatic chainepoxy resin; a glycidyl ester-type epoxy resin; a glycidyl etherifiedcondensation product of a phenol such as phenol, cresol, alkylphenol,catechol, bisphenol F, bisphenol A or bisphenol S with an aldehyde suchas formaldehyde or salicylaldehyde; a glycidyl etherified product of abifunctional phenol; a glycidyl etherified product of a bifunctionalalcohol; a glycidyl etherified product of a polyphenol; or ahydrogenated or halogenated form of any of the foregoing. Preferredamong these, from the viewpoint of heat resistance and connectionreliability, are glycidyl etherified condensation products of phenolsand aldehydes. There are no particular restrictions on the molecularweight of such (a) epoxy resins. The (a) epoxy resins may also be usedalone or in combinations of two or more.

In a liquid composition according to the first embodiment, the contentof the (a) epoxy resin is preferably selected to be such that the curingreaction completes within a prescribed heat curing time, after thecarbon black, CNT and the curing agent and optional curing acceleratorhave been added. The content of the (a) epoxy resin is preferably 1 to40 mass % and more preferably 1 to 30 mass %, as the proportion in theliquid composition. If the content is less than 1 mass % or greater than40 mass %, the viscosity will tend to be unsuitable for printing.

The liquid composition according to the second embodiment comprises (a1)a diol with a molecular weight of 40 or greater and less than 1000and/or a resin containing the diol as a backbone, and preferably also(a2) an epoxy resin with a molecular weight of between 200 and 50,000,comprising a diol with a molecular weight of 40 or greater and less than1000 in the backbone.

Examples of diols with molecular weights of 40 or greater and less than1000 include diols such as 1,2-ethanediol, 1,2-propanediol,1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol,1,4-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol,2,3-pentanediol, 2,4-pentanediol, 3,4-pentanediol, 1,5-pentanediol,1,2-hexanediol, 1,3-hexanediol, 1,4-hexanediol, 1,5-hexanediol,2,3-hexanediol, 2,4-hexanediol, 2,5-hexanediol, 3,4-hexanediol,1,6-hexanediol, 1,2-heptanediol, 1,3-heptanediol, 1,4-heptanediol,1,5-heptanediol, 1,6-heptanediol, 1,7-heptanediol, 2,3-heptanediol,2,4-heptanediol, 2,5-heptanediol, 2,6-heptanediol, 3,4-heptanediol,3,5-heptanediol and octanediol; double bond-containing diols such asbutenediol and hexenediol; and cyclic diols. The (a1) diol with amolecular weight of 40 or greater and less than 1000 and/or a resincontaining the diol as a backbone may be a diol such as mentioned aboveor its polymer, or a resin containing a diol or diol backbone, with analkyl group such as methyl or ethyl or a glycidyl ether on the ends orside chains of a diol such as mentioned above. Any of these may be usedalone or in combinations of two or more.

The diol preferably has a molecular weight of 40 or greater and lessthan 1000 in order to increase the number of functional groupscontributing to the reaction in the curing treatment during formation ofa resistor, to obtain a liquid composition with excellent curability.The molecular weight is also preferably at least 40 and less than 500,and especially less than 200, in order to further increase the number offunctional groups and the further improve the curability.

For a liquid composition according to the second embodiment, it ispreferred for the (a1) diol with a molecular weight of 40 or greater andless than 1000 and/or a resin containing the diol as a backbone, to be(a2) an epoxy resin with a molecular weight of between 200 and 50,000,comprising a diol with a molecular weight of 40 or greater and less than1000 in the backbone, as the resin comprising a diol with a molecularweight of 40 or greater and less than 1000 in the backbone. Examples forthe (a2) epoxy resin with a molecular weight of between 200 and 50,000comprising a diol with a molecular weight of 40 or greater and less than1000 in the backbone, include epoxy resins comprising residues of theaforementioned diols, and more specifically they include compoundsrepresented by the following formula (I). Any of these may be used aloneor in combinations of two or more.

In formula (I), Z¹ and Z² each independently represent a divalentorganic group, and n represents an integer of 1 or greater.

The (a2) epoxy resin comprising a diol backbone has a molecular weightof between 200 and 50,000. Using an epoxy resin with a molecular weightin this range can be expected to increase the heat resistance. Althoughthe molecular weight of the diol backbone is 40 or greater and less than1000, it is preferably 40 or greater and less than 500, and morepreferably 40 or greater and less than 200.

In a liquid composition according to the second embodiment, the contentof the (a2) epoxy resin comprising a diol backbone is preferably 10 to99 mass %, more preferably 20 to 70 mass % and even more preferably 25to 45 mass %, based on the total mass of the resin solid content in theliquid composition. If the content is less than 10 mass % the effect ofaddition will tend to be insufficiently exhibited, while if it exceeds99 mass % the heat resistance or solvent resistance of the cured productwill tend to be reduced.

A resin other than those mentioned above may also be added to liquidcompositions according to the first and second embodiments. The resinmay be any one so long as it generally exhibits electrical insulatingproperties, and examples include epoxy resins, phenol resins, polyimideresins, polyamide resins, polyamideimide resins, silicone-modifiedpolyamideimide resins, polyester resins, cyanate ester resins, BTresins, acrylic resins, melamine resins, urethane resins and alkydresins. These may be used alone or in combinations of two or more. Whensuch a resin is to be used, a thermosetting resin is preferred from theviewpoint of insulating reliability, connection reliability and heatresistance, with epoxy resins, phenol resins, polyimide resins,polyamide resins and polyamideimide resins being especially preferredfor their satisfactory mechanical properties.

Examples of epoxy resins include bisphenol A-type epoxy resins;bisphenol F-type epoxy resins; bisphenol S-type epoxy resins;biphenol-type epoxy resins; alicyclic epoxy resins; aliphatic chainepoxy resins; glycidyl ester-type epoxy resins; glycidyl etherifiedcondensation products of phenols such as phenol, cresol, alkylphenol,catechol, bisphenol F, bisphenol A and bisphenol S with aldehydes suchas formaldehyde or salicylaldehyde; glycidyl etherified products ofbifunctional phenols; glycidyl etherified products of bifunctionalalcohols; glycidyl etherified products of polyphenols; and hydrogenatedor halogenated forms of any of the foregoing. Preferred among these,from the viewpoint of heat resistance and connection reliability, areglycidyl etherified condensation products of phenols and aldehydes.There are no particular restrictions on the molecular weight of suchepoxy resins. The epoxy resins may be used alone or in combinations oftwo or more.

It is preferred to add (e) a curing agent to liquid compositions of thefirst and second embodiments. The (e) curing agent is preferably anepoxy resin curing agent. Examples for the (e) curing agent to be usedwith an epoxy resin include amines such as diethylenetriamine,triethylenetetramine, metaxylenediamine, diaminodiphenylmethane,diaminodiphenylsulfone, m-phenylenediamine and dicyandiamide; acidanhydrides such as phthalic anhydride, tetrahydrophthalic anhydride,hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride,methylhexahydrophthalic anhydride, methylnadic anhydride, pyromelliticanhydride and trimellitic anhydride; phenols such as bisphenol F,bisphenol A, bisphenol S and polyvinylphenol; condensation products ofphenols such as phenol, cresol, alkylphenol, catechol, bisphenol F,bisphenol A and bisphenol S with aldehydes such as formaldehyde andsalicylaldehyde, and halogenated forms of the foregoing. Condensationproducts of phenols and aldehydes are preferred from the viewpoint ofheat resistance and connection reliability. There are no particularrestrictions on the molecular weights of these compounds. The curingagents may also be used alone or in combinations of two or more.

The proportion of the curing agent in the epoxy resin may be aproportion used in the prior art, and it is preferably in the range of0.5 to 2.0 and more preferably 0.8 to 1.5 hydroxyl equivalents withrespect to epoxy equivalents. When the (e) curing agent isdicyandiamide, for example, it is preferably in the range of 2 to 5parts by mass with respect to 100 parts by mass of the epoxy resin.

An imidazole may also be used in a liquid composition according to thefirst or second embodiment, as a curing agent in addition to theaforementioned curing agents, or as a curing agent and an epoxy resincuring accelerator. Preferred imidazoles are those represented by thefollowing formula (1).

In formula (1), X and Y each independently represent hydrogen or asubstituent including a carbon atom, hydrogen or nitrogen atom. Theimidazole preferably satisfies either or both of the followingconditions: a side chain other than hydrogen is bonded at position X, ora C3 or greater side chain is bonded at position Y, in formula (1).Using an imidazole satisfying such conditions can inhibit increase inthe viscosity of the liquid composition.

Examples of imidazoles include imidazoles such as 2-undecylimidazole,2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole,1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole,1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole,1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole,1-cyanoethyl-2-undecylimidazolium trimellitate,1-cyanoethyl-2-phenylimidazolium trimellitate,2,4-diamino-6-[2′-methylimidazolyl-(1′)]-ethyl-s-triazine,2,4-diamino-6-[2′-undecylimidazolyl-(1′)]-ethyl-s-triazine,2,4-diamino-6-[2′-ethyl-4′-methylimidazolyl-(1′)]-ethyl-s-triazine,2,4-diamino-6-[2′-methylimidazolyl-(1′)]ethyl-s-triazineisocyanuric acidaddition product, 2-phenyl 4,5-dihydroxymethylimidazole and2-phenyl-4-methyl-5-hydroxymethylimidazole; imidazoles having the iminogroups masked with acrylonitrile, phenylene diisocyanate, toluidineisocyanate, naphthalene diisocyanate, methylene bisphenyl isocyanate,melamine acrylate or the like; and imidazoles such as 2-ethylimidazole,2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole,1-benzyl-2-methylimidazole, 2-heptadecylimidazole,4,5-diphenylimidazole, 2-methylimidazoline, 2-phenylimidazoline,2-undecylimidazoline, 2-heptadecylimidazoline, 2-isopropylimidazole,2,4-dimethylimidazole, 2-phenyl-4-methylimidazole, 2-ethylimidazoline,2-isopropylimidazoline, 2,4-dimethylimidazoline,2-phenyl-4-methylimidazoline, 1-cyanoethyl-2-methylimidazole,1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole,1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazoliumtrimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate,2-phenyl-4,5-dihydroxymethylimidazole and2-phenyl-4-methyl-5-hydroxymethylimidazole. These imidazoles may be usedalone or in combinations of two or more different types.

The proportion of such imidazoles with respect to the epoxy resin may bea proportion used in the prior art, and it is preferably in the range of0.001 to 15 parts by mass and more preferably in the range of 0.01 to 10parts by mass with respect to 100 parts by mass of the epoxy resin. Animidazole amount of less than 0.001 part by mass will tend to result incuring defects, while an amount of greater than 15 parts by mass is notpreferred because it can lead to reduced pot life of the prepared liquidcomposition.

The liquid composition according to the first embodiment comprises (d) asolvent with a vapor pressure of less than 1.34×10³ Pa at 25° C. Theliquid composition according to the second embodiment preferablycomprises (d) a solvent with a vapor pressure of less than 1.34×10³ Paat 25° C. The vapor pressure of the (d) solvent at 25° C. is preferablyat least 1.34 Pa. The (d) solvent may be any one that has a vaporpressure in the prescribed range and disperses or dissolves each of thecomponents, including the insulating resin in the liquid composition,and examples include γ-butyrolactone, N,N-dimethylformamide,N,N-dimethylacetamide and cyclohexanone.

A liquid composition according to the first or second embodiment maycontain a solvent with a vapor pressure of 1.34×10³ Pa or higher at 25°C. in addition to the (d) solvent, and the mixing proportion of thesolvent with a vapor pressure of 1.34×10³ Pa or higher is preferably nogreater than 60 mass %, more preferably no greater than 50 mass % andeven more preferably no greater than 40 mass %, based on the total massof the solvent. If the compositional ratio of the solvent is within thisrange, it will be possible to adjust the evaporation rate of the solventand lower the viscosity of the liquid composition during printing, whilealso inhibiting flow of the ink after printing. The solvent with a vaporpressure of 1.34×10³ Pa or higher at 25° C. may be any one thatdisperses or dissolves each of the components including the insulatingresin in the liquid composition, and examples include methyl isobutylketone, methyl ethyl ketone and toluene.

These solvents may be used alone or in combinations of two or more.

The viscosity of a liquid composition according to the first or secondembodiment is preferably no higher than 50 mPa·s and more preferably nohigher than 30 mPa·s at 25° C. It is not preferred for the viscosity at25° C. to exceed 50 mPa·s because the ink-jet discharge property will beimpaired. From the same viewpoint, the viscosity at 25° C. is preferablyat least 1 mPa·s.

A liquid composition according to the first or second embodiment mayalso comprise, as appropriate, other components in addition to thosementioned above, such as a curing accelerator, coupling agent,antioxidant, filler, surface control agent or the like.

A liquid composition according to the first or second embodiment may beprepared, for example, by using a disperser for dispersion of theconducting material ((b) carbon black particles and (c) CNT), in theform of a mixture of the aforementioned components other than thesolvent, or with a solvent added thereto. The disperser used may be akneader, triple roll mill, bead mill, sand mill or the like, eitheralone or in combinations. The conducting material can also be dispersedusing an apparatus equipped with an ultrasonic oscillator. Byaccomplishing dispersion using such a disperser, it is possible toadequately reduce the mean dispersion particle size of the (b) carbonblack particles. When air bubbles have been generated in the liquidcomposition after dispersion, the air bubbles are preferably removed bystanding under reduced pressure or by stirring under reduced pressure.

It is also preferred to use a dispersing agent suited for the (b) carbonblack particles or (c) CNT. This will facilitate reduction in themaximum dispersion particle size or mean dispersion particle size of the(b) carbon black particles, while also increasing the dispersionstability of the (b) carbon black particles. The dispersing agent may beany one that can disperse the (b) carbon black particles in such amanner that their maximum dispersion particle size or mean dispersionparticle size is in the prescribed range. In order to limit the maximumdispersion particle size of the (b) carbon black particles to no greaterthan 2 μm, the liquid composition may be filtered with a filter havingan opening diameter of no greater than 2 μm. This can help increase theyield when preparing the liquid composition.

A liquid composition according to the first or second embodiment,prepared as described above, can be most suitably used as a printing inkfor formation of a resistor film.

The method of forming a resistor film using the liquid composition maybe any of various printing methods, including screen printing, reliefprinting, gravure printing, ink jet printing, nanoimprinting, contactprinting, spin coat printing, or a printing method using a dispenserdevice. Particularly preferred among these is ink jet printing, becauseit allows printing of a prescribed amount of ink at prescribed locationswithout using a special plate, and because it can easily meet the needsfor material utilization efficiency and pattern design variation.

The ink jet printing method used may employ a commonly reporteddischarge process such as, for example, a piezo system wherein theliquid is discharged by vibration of a piezo element, or a thermalsystem wherein expansion of the liquid by rapid heating is utilized fordischarge of the liquid. Piezo systems are especially preferred from theviewpoint of avoiding heating the ink. Common ink-jet apparatuses may beused for such ink jet printing methods. The nozzle diameter of the headthrough which the ink is discharged may be selected as optimal for theprescribed droplet size.

A resin composite material film (resistor film) may be obtained byprinting the liquid composition on a substrate by the printing methodand then removing the solvent in the liquid composition by drying, andfinally curing the resin composition. The method for removing thesolvent after the liquid composition has been printed on the board maybe a method of heat treatment by heating the board or blowing hot aironto it. Such heat treatment may be carried out, for example, at aheating temperature of 50° C. to 250° C. for a heating time of 0.1 to2.0 hours. The resin composition may also be cured by the same method.The solvent may alternatively be removed in a vacuum environment.

The substrate is not particularly restricted so long as it is a materialcommonly used as a substrate for circuit boards. Examples of substratesthat may be used include insulating resin laminated sheets with glasscloths, insulating layers or insulating films that do not employ glasscloths, glass substrates, or metal foils such as copper foils andstainless steel foils, which may be selected depending on the purpose.In order to obtain uniform printability on the substrate, the surfacemay be cleaned or leveled by UV treatment or plasma treatment usingoxygen or argon, before the liquid composition is printed. A metalelectrode or wiring may also be formed beforehand by etching of a copperfoil on the board, or by plating, vapor deposition or sputtering.

The resin composite material film (resistor film) prepared from theliquid composition may be used as a printed resistor (resistor element).The resistance value of the printed resistor can be designed by thevolume resistivity of the resistor film and the thickness, width andlength of the resistor film to be formed. If necessary, the resistancevalue can be adjusted by trimming using a laser or the like.

Also, by performing wiring formation or mounting of active componentsand passive elements on the same board, these may be combined withresistor elements formed on a board by the printing method describedabove, for use as a circuit board.

The liquid composition of the invention can provide a material forformation of resistors with different volume resistivities withoutchanging the type of carbon black particles, since it allows the volumeresistivity to be lowered by simple addition of CNT, and it can providea material for formation of a resistor that exhibits stable volumeresistivity even after heat curing.

FIG. 1 is a perspective view showing an embodiment of a circuit boardaccording to the invention, and FIG. 2 is an end view of FIG. 1 alongline II-II. The circuit board 1 shown in FIGS. 1 and 2 comprises alaminar substrate 3 and a resistor element 5 provided on one sidethereof. The resistor element 5 has conductor films 12,12 forming a pairof electrodes and a resistor film 11 comprising a resistor formed so asto electrically connect the conductor films 12,12. The thickness of theresistor film 11 is not particularly restricted, but will typically be200 to 500,000 nm.

As mentioned above, the resistor film 11 can be formed by a method inwhich a liquid composition of the invention is printed or coated incontact with the conductor films 12 on the substrate 3 to form a film ofthe liquid composition, and the solvent is removed from the film of theliquid composition by heating. When the resin is a thermosetting resin,the resin cures as the solvent is removed. That is, the resistor film 11comprises the cured thermosetting resin and a conducting material. Aswill be understood by a person skilled in the art, the heatingconditions for forming the resistor film 11 may be appropriatelyadjusted according to the type of resin and solvent, such that thesolvent is sufficiently removed and curing of the resin sufficientlyproceeds.

The conductor film 12 is a film formed by a conductor such as copper.The method of forming the conductor film 12 is not particularlyrestricted, and for example, the conductor film 12 may be formed bycopper foil etching, copper plating, or silver wiring printing by inkjet printing.

The substrate 3 which is used may be an insulating substrate such as apaper phenol insulating sheet, glass/bismaleimide insulating sheet orglass/polyimide insulating sheet, a plastic film of polyimide orpolyethylene naphthalate to be used for a flexible circuit board, or aglass substrate.

EXAMPLES

The present invention will now be explained in more specific detailthrough the following examples, with the understanding that theinvention is in no way limited thereby.

The viscosities of the liquid compositions of the examples andcomparative examples were measured at 25° C. using a small oscillatingviscometer (trade name: CJV5000) by A&D Co., Ltd. The mean dispersionparticle size and maximum dispersion particle size of the carbon blackparticles in the liquid composition were measured at 25° C. using asubmicron particle analyzer (Model N5) by Beckman Coulter, Inc. Thevolume resistivity of the cured liquid composition was measured using aLORESTA GP (trade name) by Mitsubishi Chemical Corp.

Example 1-1

A 100 g portion of a carbon black slurry (carbon black particle content:20 mass %, mean dispersion particle size: 115 nm, maximum dispersionparticle size: 300 nm), obtained by dispersing carbon black particles(mean primary particle size: approximately 20 nm) in gamma-butyrolactone(25° C. vapor pressure: 2.3×10² Pa), was added to a resin solutioncomprising a mixture of 13.5 g of gamma-butyrolactone, 5.9 g of an epoxyresin (trade name: N-865 by DIC), 3.2 g of a phenol resin (trade name:VH-4170 by DIC) and 0.44 g of 1-cyanoethyl-2-methylimidazole (TokyoKasei Kogyo Co., Ltd.), and these were mixed to obtain a liquid mixture.To the liquid mixture there was added a CNT dispersion (CNT content: 2mass %) which was a dispersion of carbon nanotubes (CNT) (outerdiameter: 10-30 nm, length: 100-1000 nm) in gamma-butyrolactone, in anamount of 3 parts by mass (0.6 g) of CNT to 100 parts by mass of thecarbon black particles, to obtain a liquid composition with a viscosityof 15 mPa·s, and carbon black particles with a mean dispersion particlesize of 130 nm and a maximum dispersion particle size of 300 nm.

Example 1-2

A liquid composition with a viscosity of 18 mPa·s and having carbonblack particles with a mean dispersion particle size of 140 nm and amaximum dispersion particle size of 300 nm was obtained by the samemethod as Example 1-1, except that for preparation of a liquid mixture,the amount of carbon black slurry was 110 g and the amount ofgamma-butyrolactone was 12 g, and the amount of CNT dispersion added tothe liquid mixture was adjusted so that the amount of CNT was 0.65 g (3parts by mass of CNT with respect to 100 parts by mass of carbon blackparticles).

Comparative Example 1-1

A liquid composition with a viscosity of 15 mPa·s and having carbonblack particles with a mean dispersion particle size of 130 nm and amaximum dispersion particle size of 300 nm was obtained by the samemethod as Example 1-1, except that no CNT dispersion was added.

Comparative Example 1-2

A liquid composition with a viscosity of 18 mPa·s and having carbonblack particles with a mean dispersion particle size of 140 nm and amaximum dispersion particle size of 300 nm was obtained by the samemethod as Example 1-2, except that no CNT dispersion was added.

Comparative Example 1-3

A liquid composition with a viscosity of 12 mPa·s and having carbonblack particles with a mean dispersion particle size of 140 nm and amaximum dispersion particle size of 300 nm was obtained by the samemethod as Example 1-1, except that the solvent used was methyl ethylketone (26° C. vapor pressure: 1.3×10⁴ Pa) instead ofgamma-butyrolactone.

Comparative Example 1-4

A liquid composition with a viscosity of 14 mPa·s and having carbonblack particles with a mean dispersion particle size of 140 nm and amaximum dispersion particle size of 300 nm was obtained by the samemethod as Example 1-1, except that the solvent used was methyl isobutylketone (22° C. vapor pressure: 2.2×10³ Pa) instead ofgamma-butyrolactone.

(Printing Evaluation)

When the liquid compositions obtained in Examples 1-1 and 1-2 andComparative Examples 1-1 to 1-4 were printed with an ink jet printingdevice, it was found that the liquid compositions of Examples 1-1 and1-2 and Comparative Examples 1-1 and 1-2 could be satisfactorily coatedwithout clogging of the ink-jet head. In contrast, with the liquidcomposition obtained in Comparative Example 1-3, clogging of the ink-jethead occurred and coating could not be accomplished. Also, whileclogging did not occur for a short period with the liquid compositionobtained in Comparative Example 1-4, after being left in anon-discharging state for more than 60 minutes and having repeateddischarge, some nozzles were incapable of initial discharge.

(Measurement of Volume Resistivity)

The liquid compositions obtained in Examples 1-1 and 1-2 and ComparativeExamples 1-1 and 1-2 were sampled in an amount of 100 μL with amicropipette and dropped onto a glass plate. The samples were heat curedfor a prescribed time at 210° C. The volume resistivities of the curedproducts were measured at heat curing times of 1, 2, 3, 4.5 and 5.5hours, producing the results shown in FIG. 3. As a result, with theliquid compositions of Examples 1-1 and 1-2, stable, low volumeresistivity was obtained with low variation in volume resistivity evenwhen the heating time was further extended beyond 1 hour, whereas withthe liquid compositions of Comparative Examples 1-1 and 1-2, the volumeresistivity varied with time and the volume resistivity was higher thanin the examples.

Example 2-1

A 100 g portion of a carbon black slurry (carbon black particle content:20 mass %, mean dispersion particle size: 115 nm, maximum dispersionparticle size: 300 nm), obtained by dispersing carbon black particles(mean primary particle size: approximately 20 nm) in gamma-butyrolactone(25° C. vapor pressure: 2.3×10² Pa), was added to a resin solutioncomprising a mixture of 13.5 g of gamma-butyrolactone, 6.1 g of an epoxyresin with a molecular weight of 900, comprising a diol backbone with amolecular weight of 40 or greater and less than 1000 (trade name:EXA4850-150 by DIC), 1.6 g of a phenol resin (trade name: VH-4170 byDIC) and 0.47 g of 1-cyanoethyl-2-methylimidazole (Tokyo Kasei KogyoCo., Ltd.), and these were mixed to obtain a liquid composition with aviscosity of 15 mPa·s and having carbon black particles with a meandispersion particle size of 140 nm and a maximum dispersion particlesize of 300 nm.

Example 2-2

To the liquid composition obtained in Example 2-1 there was added a CNTdispersion (CNT content: 2 mass %) which was a dispersion of carbonnanotubes (CNT) (outer diameter: 10-30 nm, length: 100-1000 nm) ingamma-butyrolactone, in an amount of 3 parts by mass (0.6 g) of CNT to100 parts by mass of the carbon black particles, to obtain a liquidcomposition with a viscosity of 17 mPa·s, and carbon black particleswith a mean dispersion particle size of 130 nm and a maximum dispersionparticle size of 300 nm.

Comparative Example 2-1

A 100 g portion of a carbon black slurry (carbon black particle content:20 mass %, mean dispersion particle size: 115 nm, maximum dispersionparticle size: 300 nm), obtained by dispersing carbon black particles ingamma-butyrolactone was added to a resin solution comprising a mixtureof 13.5 g of gamma-butyrolactone, 5.9 g of a bisphenol A-novolac-typeepoxy resin comprising no diol backbone (trade name: N865 by DIC), 3.2 gof a phenol resin (trade name: VH-4170 by DIC) and 0.44 g of1-cyanoethyl-2-methylimidazole (Tokyo Kasei Kogyo Co., Ltd.), and thesewere mixed to obtain a liquid composition with a viscosity of 15 mPa·sand having carbon black particles with a mean dispersion particle sizeof 130 nm and a maximum dispersion particle size of 300 nm.

Comparative Example 2-2

A liquid composition with a viscosity of 20 mPa·s and having carbonblack particles with a mean dispersion particle size of 130 nm and amaximum dispersion particle size of 300 nm was obtained by the samemethod as Comparative Example 2-1, except that the amount of carbonblack slurry was 110 g and the amount of gamma-butyrolactone was 11.9 g.

(Printing Evaluation)

When the liquid compositions obtained in Examples 2-1 and 2-2 andComparative Examples 2-1 and 2-2 were printed with an ink jet printingdevice, it was found that they could be satisfactorily coated withoutclogging of the ink-jet head.

(Measurement of Volume Resistivity)

The liquid compositions obtained in Examples 2-1 and 2-2 and ComparativeExamples 2-1 and 2-2 were sampled in an amount of 100 μL with amicropipette and dropped onto a glass plate. The samples were heat curedfor a prescribed time at 210° C. The volume resistivities of the curedproducts were measured at heat curing times of 1, 2, 3, 4.5 and 5.5hours, producing the results shown in FIG. 4. As a result, with theliquid compositions of Examples 2-1 and 2-2, the variation in volumeresistivity was low even when the heating time was further extendedbeyond 2 hours, while stable, low volume resistivity was obtained for 2hours thereafter, whereas with the liquid compositions of ComparativeExamples 2-1 and 2-2, the volume resistivity varied with time and thevolume resistivity was higher than in the examples. With the liquidcomposition of Example 2-2, it was confirmed that the stabilization timefor the volume resistivity was more rapid than with the liquidcomposition of Example 2-1.

INDUSTRIAL APPLICABILITY

According to the invention it is possible to obtain a liquid compositionthat is suitable for forming resistors by ink jet printing and that canexhibit a stable resistance value, as well as a resistor film, resistorelement and circuit board using the liquid composition.

EXPLANATION OF SYMBOLS

1: Circuit board, 3: substrate, 5: resistor element, 11: resistor film,12: conductor film.

1. A liquid composition comprising (a) an epoxy resin, (b) carbon blackparticles, (c) carbon nanotubes and (d) a solvent with a vapor pressureof less than 1.34×10³ Pa at 25° C.
 2. The liquid composition accordingto claim 1, wherein the mean dispersion particle size of the (b) carbonblack particles is no greater than 500 nm, and the maximum dispersionparticle size is no greater than 2 μm.
 3. The liquid compositionaccording to claim 1, wherein the outer diameter of the (c) carbonnanotubes is 3 nm or greater and the length is 100 nm or greater.
 4. Theliquid composition according to claim 1, wherein the content of the (b)carbon black particles is 10 to 80 vol %, based on the total solidvolume of the liquid composition.
 5. The liquid composition according toclaim 1, wherein the content of the (c) carbon nanotubes is 0.1 to 20parts by mass with respect to 100 parts by solid mass of the (b) carbonblack particles.
 6. The liquid composition according to claim 1, whereinthe viscosity is no greater than 50 mPa·s at 25° C.
 7. The liquidcomposition according to claim 1, wherein the (a) epoxy resin is aglycidyl etherified condensation product of a phenol and an aldehyde. 8.The liquid composition according to claim 1, which further comprises (e)a curing agent, the (e) curing agent comprising the condensation productof a phenol and an aldehyde.
 9. A liquid composition comprising (a1) adiol with a molecular weight of 40 or greater and less than 1000 and/ora resin containing the diol as a backbone, and (b) carbon blackparticles.
 10. The liquid composition according to claim 9, wherein the(a1) diol with a molecular weight of 40 or greater and less than 1000and/or a resin containing the diol as a backbone includes (a2) an epoxyresin with a molecular weight of between 200 and 50,000, comprising adiol with a molecular weight of 40 or greater and less than 1000 in thebackbone.
 11. The liquid composition according to claim 9, which furthercomprises (d) a solvent with a vapor pressure of less than 1.34×10³ Paat 25° C., and (e) a curing agent.
 12. The liquid composition accordingto claim 11, wherein the (e) curing agent comprises the condensationproduct of a phenol and an aldehyde.
 13. The liquid compositionaccording to claim 9, wherein the mean dispersion particle size of the(b) carbon black particles is no greater than 500 nm, and the maximumdispersion particle size is no greater than 2 μm.
 14. The liquidcomposition according to claim 9, wherein the content of the (b) carbonblack particles is 10 to 80 vol %, based on the total solid volume ofthe liquid composition.
 15. The liquid composition according to claim 9,wherein the viscosity is no greater than 50 mPa·s at 25° C.
 16. Theliquid composition according to claim 9, which further comprises (c)carbon nanotubes.
 17. The liquid composition according to claim 16,wherein the outer diameter of the (c) carbon nanotubes is 3 nm orgreater and the length is 100 nm or greater.
 18. The liquid compositionaccording to claim 16, wherein the content of the (c) carbon nanotubesis 0.1 to 20 parts by mass with respect to 100 parts by solid mass ofthe (b) carbon black particles.
 19. A resistor film formed by removingthe solvent from the liquid composition according to claim 1 by heating.20. A resistor film formed by printing or coating the liquid compositionaccording to claim 1 on a substrate to form a film of the liquidcomposition, and removing the solvent from the film of the liquidcomposition by heating.
 21. A resistor element having the resistor filmaccording to claim
 19. 22. A circuit board having the resistor elementaccording to claim 21 formed on a substrate.
 23. A resistor elementhaving the resistor film according to claim
 20. 24. A circuit boardhaving the resistor element according to claim 23 formed on a substrate.25. A resistor film formed by removing the solvent from the liquidcomposition according to claim 9 by heating.
 26. A resistor film formedby printing or coating the liquid composition according to claim 9 on asubstrate to form a film of the liquid composition, and removing thesolvent from the film of the liquid composition by heating.
 27. Aresistor element having the resistor film according to claim
 25. 28. Acircuit board having the resistor element according to claim 27 formedon a substrate.
 29. A resistor element having the resistor filmaccording to claim
 26. 30. A circuit board having the resistor elementaccording to claim 29 formed on a substrate.